CN105396590A - Method for preparing ozonation catalyst by scrap iron surface modifying, and application of ozonation catalyst - Google Patents

Method for preparing ozonation catalyst by scrap iron surface modifying, and application of ozonation catalyst Download PDF

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Publication number
CN105396590A
CN105396590A CN201510733013.4A CN201510733013A CN105396590A CN 105396590 A CN105396590 A CN 105396590A CN 201510733013 A CN201510733013 A CN 201510733013A CN 105396590 A CN105396590 A CN 105396590A
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iron filings
iron
catalyst
ozone
oxyhydroxide
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马鲁铭
马捷汀
陈林
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Nanjing Mingning Water Treatment Technology Co Ltd
Tongji University
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Nanjing Mingning Water Treatment Technology Co Ltd
Tongji University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/12—Oxidising
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Materials Engineering (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

The invention relates to a method for preparing an ozonation catalyst by scrap iron surface modifying. The method comprises: (1) forming a passivation layer on the scrap iron surface by chemical modifying, wherein the main component is oxyhydroxide of iron, and is described by FexOyHz (z is greater than 1), so that a heterogeneous catalysis oxidation mechanism to O3 is formed; and (2) performing long-term oxidation on scrap iron not subjected to surface strong acid and strong alkali modifying in wastewater by O3 to obtain the same oxyhydroxide of iron which is described by FexOyHz (z is greater than 1). When the catalyst prepared by the method disclosed in the invention is used for catalyzing ozonation, the removal rate of second-stage biochemical treatment effluent COD in common industrial wastewater is 50-80%, so that new national emission standard requirements can be met, and the application value can not be influenced.

Description

A kind of iron filings surface modification prepares method and the application thereof of ozone oxidation catalyst
Technical field
The present invention relates to field of water pollution control, be specifically related to a kind of method that iron filings surface modification prepares ozone oxidation catalyst.
Background technology
The application of ozone in water treatment has longer history.In Water purification field: ozone, as disinfectant, effectively can kill sex pheromone, and the chloro DBPs with producing during disinfection by chlorine can being avoided, having formed ripe ozonization technique; Ozone is added in the front end of biological activated carbon, can play the effect of algae removal deodorizing, the larger molecular organics simultaneously will existed in natural water, oxidation Decomposition is small organic molecule, help the degraded of microorganism in subsequent bio active carbon, define Ozone-Biological Activated Carbon Process.At sewage treatment area: the oxidability utilizing ozone self, the organic functional group of oxidized portion, or part long-chain macromolecule organic substance decomposing is become short chain small organic molecule, to improve organic biodegradable, existing a large amount of achievement in research and a small amount of engineering practice are confirmed.But ozone autoxidation ability is more weak, can not degradable organic matter, and partial organic substances is after ozone incomplete oxidation, molecule functional group changes, and bio-toxicity is stronger, limits the application of ozone as industrial wastewater Biological Pretreatment.Bring out ozone and produce hydroxyl radical free radical, thus form advanced oxidation mechanism, thorough decomposing organic matter, becomes study hotspot quite over a long time, but ozone formation advanced oxidation mechanism needs pH value strong alkaline condition, or needs and hydrogen peroxide (H 2o 2), ultraviolet (UV) coupling, or need metal oxide containing precious metals catalysis (as Ti 2o), though existing large quantifier elimination, engineer applied is small.
At present, China's Industrial Wastewater Treatment standard is more strict, and biological treatment (two stage treatment) technique cannot reach discharge standard, and the selection of its advanced treatment process, advanced oxidation processes almost becomes only option.And in current industrial waste water treatment engineering, ozonation technology lacks means of catalysis, greatly reduce the efficiency of ozone process, advanced treating effect is very undesirable.
By adding hydrogen peroxide (H 2o 2) or use ultraviolet (UV) to irradiate, bring out ozone and form advanced oxidation mechanism, its condition is comparatively harsh, and cost is high, is not suitable for that the water yield is large, pH value is neutral city and the advanced treating of industrial park Sewage Plant secondary biochemical effluent.There are some researches show: the oxyhydroxide of iron is (with Fe xo yh z(z>1) represent, typically have FeOOH) catalysis O in aqueous 3effective, be desirable catalyst.But the oxyhydroxide of iron is generally react with water in an oxidizing environment to be formed, and produces the catalyst cost with fixing crystal formation and molecular structure higher.
Iron filings are refuses that intermetallic composite coating produces, and wide material sources are cheap.Although iron filings source is different, composition is also variant, but due to the ductility difference of different steel, the iron filings forming more complete wood shavings shape mostly belong to carbon steel and low-alloy steel, mainly contain: the mild steel in carbon structural steel, carbon constructional quality steel and medium carbon steel and low-alloy structural steel by steel classification.The iron plane flower of these steel, have stronger chemical reactivity, surface is more oxidizable, is expected to form O under certain condition 3the catalysis material of advanced oxidization method; And corrosion-resistant stainless steel chemical reactivity is very low, discomfort is used as catalysis O 3catalysis material, though stainless steel forms wood shavings, but color and luster has notable difference; Because price difference is huge, be not easily mixed in common iron filings.
Therefore, use iron filings are raw material, by suitable physics and chemical method to iron filings modifying surface, make it surface and form catalysis O 3active ingredient, namely formed and there is the Fe of certain chemical composition and crystalline structure xo yh z(z>1), described material is the feasible way reducing advanced oxidization method catalyst cost, has important practical value.
In iron filings, the content of ferro element is general all more than 98%, and because the chemism of iron is comparatively strong, the iron filings of unpassivated are easily oxidized in containing the waste water of ozone, and formation FeOOH purification layer, becomes a certain amount of iron ion simultaneously.Although iron ion also can catalysis O 3, but belonging to homogeneous catalysis process, catalyst consumes, and can not reclaim.Because the iron ion generated is coagulant composition, in pH neutral range, Fe (III) all precipitates, and does not only produce adverse effect to water quality, and forms advanced treatment process again.
Summary of the invention
The object of the invention is to a kind of method that iron filings surface modification prepares ozone oxidation catalyst.Catalyst prepared by the inventive method, is adapted to the advanced treating of two stage biological process water outlet, and advantage is the pH value not changing waste water, and do not increase salinity and other composition of waste water, the degree of depth removes the organic matter in waste water.
Thinking of the present invention is: (1), in strong acid or strong alkali aqueous solution, form purification layer by oxidation (oxygen uptake corrosion) on iron filings surface, its main component is the oxyhydroxide of iron, with Fe xo yh z(z>1) represent, thus formed O 3heterocatalysis oxidation catalysis composition, complete material modification; (2) iron filings of long time without surface modification, O in waste water 3during oxidation, the oxyhydroxide of iron can be formed equally, but a certain amount of iron ion can be formed simultaneously, cause the loss of iron filings; (3) iron ion produced in actual application can be used as coagulant, and by adding flocculation aid, form coagulating sedimentation or contact filtration mechanism, not only iron ion is removed, and can remove the organic matter in water further.
The iron filings surface modification that the present invention proposes prepares the method for ozone oxidation catalyst, and concrete steps are as follows:
(1) choose the waste material iron filings produced in intermetallic composite coating, degreasing and rust removal pretreatment is carried out to it;
(2) iron filings step (1) obtained use strong acid or highly basic modification, obtain described ozone oxidation catalyst; Described strong acid adopts nitric acid or sulfuric acid, and described highly basic adopts NaOH;
Adopt Nitric Acid Modified: be positioned in open containers by the iron filings that step (1) obtains and use HNO 3soak, described open containers is positioned on shaking table, and described iron filings pass through HNO 3passivation reaction 0.5 ~ 3.0hr, cleaning-drying after taking out; Modified iron filings surface forms the oxyhydroxide of a certain amount of iron, with Fe xo yh z(z>1) represent; Described HNO 3concentration be the HNO of 65%-68% 3;
Adopt sulfuric acid modified: the iron filings that step (1) obtains are positioned in open containers and use H 2sO 4soak, described open containers is positioned on shaking table, and described iron filings pass through H 2sO 4passivation reaction 1.0 ~ 5.0hr, cleaning-drying after taking out; Modified iron filings surface forms the oxyhydroxide of a certain amount of iron, with Fe xo yh z(z>1) represent; Described H 2sO 4concentration be the H of 98% 2sO 4;
Adopt NaOH modification; Be positioned over by the iron filings that step (1) obtains in open containers and soak by NaOH solution, described iron filings, by NaOH solution passivation reaction 1.0 ~ 10.0hr, take out rear cleaning-drying; Modified iron filings surface forms the oxyhydroxide of a certain amount of iron, with Fe xo yh z(z>1) represent; The concentration of described NaOH solution is 30%.
The ozone oxidation catalyst that the method that iron filings surface modification prepares ozone oxidation catalyst obtains, for the manufacture of a catalyst oxidation reactor, is specially: bulk density is compressed to 50 ~ 500kg/M by using hydraulic press by ozone oxidation catalyst 3form fixing filler reaction bed, ozone distribution device is placed in below filler; Even at guarantee water distribution, when there is not the short stream of current, control hydraulic detention time and equal the catalytic oxidation time, be generally 10 ~ 40 minutes; Form catalyst oxidation reactor thus.
The ozone oxidation catalyst that a kind of method that iron filings surface modification prepares ozone oxidation catalyst obtains is for the manufacture of catalyst oxidation reactor, be specially: bulk density, as ozone oxidation catalyst, is compressed to 50 ~ 500kg/M by using hydraulic press by iron filings step (1) obtained 3form fixing filler reaction bed, ozone distribution device is placed in below filler; Even at guarantee water distribution, when there is not the short stream of current, control hydraulic detention time and equal the catalytic oxidation time, be generally 10 ~ 40 minutes; Form catalyst oxidation reactor thus.
Beneficial effect of the present invention is: (1) catalyst price is very cheap.Relative to the catalyst of catalysis ozone containing elements such as Ti, Co, Mn, Ni, material cost greatly reduces.(2) be applicable to the neutral waste water of pH, do not need to regulate acid-base value, do not increase waste water salinity, there is no heavy metal pollution risk; The iron hydroxylate wherein generated, can form coagulating sedimentation or contact filtration unit, favourable to further organics removal.(3) iron filings in use have " autocatalysis ", that is: constantly form the oxyhydroxide of iron, with Fe xo yh z(z>1) represent, therefore in use procedure, catalytic effect can not reduce; The measures such as backwash can be taked in technique to remove the dirty layer on catalysis material surface, and catalytic performance is unaffected, therefore has very high engineering feasibility.
Detailed description of the invention
The present invention is further illustrated below by embodiment.
Embodiment 1: red fuming nitric acid (RFNA) is passivating modified in short-term
(1) choose the waste material iron filings produced in intermetallic composite coating, pretreatment is carried out to it; Described pretreatment refers to the soil conditions according to iron filings surface, uses the NaOH of 1mol/L to wash away the greasy of iron filings surface, uses the H of 1% 2sO 4wash away the iron rust on iron filings surface.
Get the iron filings after step (1) degreasing and rust removal, working concentration is the HNO of 68% 3soak, shaking table is immersed in passivation reaction 0.5hr in open containers, cleaning-drying after taking out, surface forms the dense film of the oxyhydroxide composition of iron, is prepared into catalyst Fe xo yh z(z>1);
Catalysis O 3oxidation susceptibility: certain chemical industrial park sewage treatment plant secondary biochemical effluent, COD is 135mg/L.O 3the catalytic oxidation pond time of staying is 20min; O 3dosage is 85mg/L, and catalyst buildup density is 200kg/M 3.After catalytic oxidation, COD is 60mg/L, and clearance reaches 55%, and forming iron compound total iron is 40mg/L.Follow-up coagulating sedimentation unit, adding PAM is 1mg/L, and water outlet COD is 55mg/L, and total iron is less than 2.0mg/L.
Embodiment 2: passivating modified when red fuming nitric acid (RFNA) is long
Step (1) is with embodiment step (1).
Get the iron filings after step (1) degreasing and rust removal, working concentration is the HNO of 68% 3soak, shaking table is immersed in passivation reaction 3.0hr in open containers, cleaning-drying after taking out, surface forms the dense film be made up of the oxyhydroxide of iron, is prepared into catalyst Fe xo yh z(z>1);
Catalysis O 3oxidation susceptibility: certain chemical industrial park sewage treatment plant secondary biochemical effluent, COD is 140mg/L.O 3the catalytic oxidation pond time of staying is 20min; O 3dosage is 100mg/L, and catalyst buildup density is 200kg/M 3.After catalytic oxidation, COD is 50mg/L, and clearance reaches 64%, and forming iron compound total iron is 20mg/L.Follow-up coagulating sedimentation unit, adding PAM is 1mg/L, and water outlet COD is 48mg/L, and total iron is less than 2.0mg/L.
Embodiment 3: the concentrated sulfuric acid is passivating modified in short-term
Step (1) is with embodiment step (1).
Get the iron filings after step (1) degreasing and rust removal, working concentration is the H of 98% 2sO 4soak, shaking table is immersed in passivation reaction 0.5hr in open containers, cleaning-drying after taking out, surface forms the dense film be made up of the oxyhydroxide of iron, is prepared into catalyst Fe xo yh z(z>1);
Catalysis O 3oxidation susceptibility: certain chemical industrial park sewage treatment plant secondary biochemical effluent, COD is 130mg/L.O 3the catalytic oxidation pond time of staying is 20min; O 3dosage is 90mg/L, and catalyst buildup density is 200kg/M 3.After catalytic oxidation, COD is 65mg/L, and clearance reaches 50%, and forming iron compound total iron is 45mg/L.Follow-up coagulating sedimentation unit, adding PAM is 1mg/L, and water outlet COD is 60mg/L, and total iron is less than 2.0mg/L.
Embodiment 4: passivating modified when the concentrated sulfuric acid is long
Step (1) is with embodiment step (1).
Get the iron filings after step (1) degreasing and rust removal, working concentration is the H of 98% 2sO 4soak, shaking table is immersed in passivation reaction 5.0hr in open containers, cleaning-drying after taking out, surface forms the dense film be made up of the oxyhydroxide of iron, is prepared into catalyst Fe xo yh z(z>1);
Catalysis O 3oxidation susceptibility: certain chemical industrial park sewage treatment plant secondary biochemical effluent, COD is 140mg/L.O 3the catalytic oxidation pond time of staying is 20min; O 3dosage is 95mg/L, and catalyst buildup density is 200kg/M 3.After catalytic oxidation, COD is 56mg/L, and clearance reaches 60%, and forming iron compound total iron is 20mg/L.Follow-up coagulating sedimentation unit, adding PAM is 1mg/L, and water outlet COD is 50mg/L, and total iron is less than 2.0mg/L.
Embodiment 5: highly basic is passivating modified in short-term
Step (1) is with embodiment step (1).
Get the iron filings after step (1) degreasing and rust removal, working concentration is the NaOH solution immersion of 30%, shaking table is immersed in passivation reaction 1.0hr in open containers, cleaning-drying after taking out, surface forms the dense film be made up of the oxyhydroxide of iron, is prepared into catalyst Fe xo yh z(z>1);
Catalysis O 3oxidation susceptibility: certain chemical industrial park sewage treatment plant secondary biochemical effluent, COD is 135mg/L.O 3the catalytic oxidation pond time of staying is 20min; O 3dosage is 100mg/L, and catalyst buildup density is 200kg/M 3.After catalytic oxidation, COD is 48mg/L, and clearance reaches 64%, and forming iron compound total iron is 20mg/L.Subsequent touch filter element, adding PAM is 1mg/L, and water outlet COD is 45mg/L, and total iron is less than 1.0mg/L.
Embodiment 6: passivating modified when highly basic is long
Step (1) is with embodiment step (1).
Get the iron filings after step (1) degreasing and rust removal, working concentration is the NaOH solution immersion of 30%, shaking table is immersed in passivation reaction 10.0hr in open containers, cleaning-drying after taking out, surface forms the dense film be made up of the oxyhydroxide of iron, is prepared into catalyst Fe xo yh z(z>1);
Catalysis O 3oxidation susceptibility: certain chemical industrial park sewage treatment plant secondary biochemical effluent, COD is 140mg/L.O 3the catalytic oxidation pond time of staying is 20min; O 3dosage is 105mg/L, and catalyst buildup density is 200kg/M 3.After catalytic oxidation, COD is 42mg/L, and clearance reaches 70%, and forming iron compound total iron is 15mg/L.Subsequent touch filter element, adding PAM is 1mg/L, and water outlet COD is 40mg/L, and total iron is less than 1.0mg/L.
Embodiment 7: iron filings are unmodified
Step (1) is with embodiment step (1).
Get the iron filings after step (1) degreasing and rust removal, directly use as ozone catalyst;
Catalysis O 3oxidation susceptibility: certain chemical industrial park sewage treatment plant secondary biochemical effluent, COD is 120mg/L.O 3the catalytic oxidation pond time of staying is 20min; O 3dosage is 120mg/L, and catalyst buildup density is 200kg/M 3.After catalytic oxidation, COD is 66mg/L, and clearance is 45%, forms iron compound total iron up to 80mg/L.Follow-up coagulating sedimentation unit, adding PAM is 1.5mg/L, and water outlet COD is 60mg/L, and total iron is less than 2.0mg/L.
Embodiment 8: catalytic performance after unmodified iron filings Long-Time Service
Step (1) is with embodiment step (1).
Get the iron filings after step (1) degreasing and rust removal, use as ozone catalyst, after using 120hr, performance is basicly stable, forms the oxyhydroxide of a certain amount of iron, with Fe on surface xo yh z(z>1) represent.
Catalysis O 3oxidation susceptibility: certain chemical industrial park sewage treatment plant secondary biochemical effluent, COD is 120mg/L.O 3the catalytic oxidation pond time of staying is 20min; O 3dosage is 110mg/L, and catalyst buildup density is 200kg/M 3.After catalytic oxidation, COD is 60mg/L, and clearance is 50%, forms iron compound total iron and reaches 50mg/L.Follow-up coagulating sedimentation unit, adding PAM is 1.5mg/L, and water outlet COD is 58mg/L, and total iron is less than 2.0mg/L.

Claims (3)

1. iron filings surface modification prepares the method for ozone oxidation catalyst, it is characterized in that concrete steps are as follows:
(1) choose the waste material iron filings produced in intermetallic composite coating, degreasing and rust removal pretreatment is carried out to it;
(2) iron filings step (1) obtained use strong acid or highly basic modification, obtain described ozone oxidation catalyst; Described strong acid adopts nitric acid-sulfuric acid, and described highly basic adopts NaOH;
Adopt Nitric Acid Modified: be positioned in open containers by the iron filings that step (1) obtains and use HNO 3soak, described open containers is positioned on shaking table, and described iron filings pass through HNO 3passivation reaction 0.5 ~ 3.0hr, cleaning-drying after taking out; Modified iron filings surface forms the oxyhydroxide of a certain amount of iron, with Fe xo yh z(z>1) represent; Described HNO 3concentration be the HNO of 65%-68% 3;
Adopt sulfuric acid modified: the iron filings that step (1) obtains are positioned in open containers and use H 2sO 4soak, described open containers is positioned on shaking table, and described iron filings pass through H 2sO 4passivation reaction 1.0 ~ 5.0hr, cleaning-drying after taking out; Modified iron filings surface forms the oxyhydroxide of a certain amount of iron, with Fe xo yh z(z>1) represent; Described H 2sO 4concentration be the H of 98% 2sO 4;
Adopt NaOH modification; Be positioned over by the iron filings that step (1) obtains in open containers and soak by NaOH solution, described iron filings, by NaOH solution passivation reaction 1.0 ~ 10.0hr, take out rear cleaning-drying; Modified iron filings surface forms the oxyhydroxide of a certain amount of iron, with Fe xo yh z(z>1) represent; The concentration of described NaOH solution is 30%.
2. the ozone oxidation catalyst that the method that iron filings surface modification as claimed in claim 1 prepares ozone oxidation catalyst obtains, for the manufacture of a catalyst oxidation reactor, is characterized in that being specially: bulk density is compressed to 50 ~ 500kg/M by using hydraulic press by ozone oxidation catalyst 3form fixing filler reaction bed, ozone distribution device is placed in below filler; Even at guarantee water distribution, when there is not the short stream of current, control hydraulic detention time and equal the catalytic oxidation time, be generally 10 ~ 40 minutes; Form catalyst oxidation reactor thus.
3. the ozone oxidation catalyst that the method that an iron filings surface modification as claimed in claim 1 prepares ozone oxidation catalyst obtains is for the manufacture of catalyst oxidation reactor, it is characterized in that being specially: bulk density, as ozone oxidation catalyst, is compressed to 50 ~ 500kg/M by using hydraulic press by iron filings step (1) obtained 3form fixing filler reaction bed, ozone distribution device is placed in below filler; Even at guarantee water distribution, when there is not the short stream of current, control hydraulic detention time and equal the catalytic oxidation time, be generally 10 ~ 40 minutes; Form catalyst oxidation reactor thus.
CN201510733013.4A 2015-11-03 2015-11-03 Method for preparing ozonation catalyst by scrap iron surface modifying, and application of ozonation catalyst Pending CN105396590A (en)

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CN107199037A (en) * 2017-06-28 2017-09-26 同济大学 A kind of Cu/Fe bimetallic materials surface is modified the preparation method of ozone catalyst
CN112427005A (en) * 2020-10-31 2021-03-02 同济大学 Micro-channel whole-building filler for catalyzing ozone to form advanced oxidation
CN112759064A (en) * 2021-01-04 2021-05-07 华东理工大学 Ozone catalytic oxidation system and treatment method of coal chemical industry concentrated solution

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107199037A (en) * 2017-06-28 2017-09-26 同济大学 A kind of Cu/Fe bimetallic materials surface is modified the preparation method of ozone catalyst
CN112427005A (en) * 2020-10-31 2021-03-02 同济大学 Micro-channel whole-building filler for catalyzing ozone to form advanced oxidation
CN112427005B (en) * 2020-10-31 2021-09-03 同济大学 Micro-channel whole-building filler for catalyzing ozone to form advanced oxidation
CN112759064A (en) * 2021-01-04 2021-05-07 华东理工大学 Ozone catalytic oxidation system and treatment method of coal chemical industry concentrated solution

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